CN113490559B - Three-dimensional printing with blocked polyisocyanates - Google Patents
Three-dimensional printing with blocked polyisocyanates Download PDFInfo
- Publication number
- CN113490559B CN113490559B CN201980093421.4A CN201980093421A CN113490559B CN 113490559 B CN113490559 B CN 113490559B CN 201980093421 A CN201980093421 A CN 201980093421A CN 113490559 B CN113490559 B CN 113490559B
- Authority
- CN
- China
- Prior art keywords
- binder
- build material
- dimensional printing
- metal particles
- blocked isocyanate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000010146 3D printing Methods 0.000 title claims abstract description 55
- 229920001228 polyisocyanate Polymers 0.000 title claims abstract description 49
- 239000005056 polyisocyanate Substances 0.000 title claims abstract description 49
- 239000000463 material Substances 0.000 claims abstract description 129
- 239000011230 binding agent Substances 0.000 claims abstract description 107
- 229920005862 polyol Polymers 0.000 claims abstract description 59
- 150000003077 polyols Chemical class 0.000 claims abstract description 53
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000002923 metal particle Substances 0.000 claims abstract description 49
- 230000000903 blocking effect Effects 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims description 45
- 239000000203 mixture Substances 0.000 claims description 21
- 238000005245 sintering Methods 0.000 claims description 19
- 238000009826 distribution Methods 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 15
- 239000000853 adhesive Substances 0.000 claims description 12
- 230000001070 adhesive effect Effects 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000012530 fluid Substances 0.000 claims description 9
- 239000010935 stainless steel Substances 0.000 claims description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims description 9
- 150000001721 carbon Chemical group 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 3
- 229910000677 High-carbon steel Inorganic materials 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001315 Tool steel Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 150000003951 lactams Chemical class 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 150000002923 oximes Chemical class 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 150000003949 imides Chemical class 0.000 claims description 2
- UBQKCCHYAOITMY-UHFFFAOYSA-N pyridin-2-ol Chemical compound OC1=CC=CC=N1 UBQKCCHYAOITMY-UHFFFAOYSA-N 0.000 claims description 2
- WHMDPDGBKYUEMW-UHFFFAOYSA-N pyridine-2-thiol Chemical compound SC1=CC=CC=N1 WHMDPDGBKYUEMW-UHFFFAOYSA-N 0.000 claims description 2
- 150000003573 thiols Chemical class 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 238000003776 cleavage reaction Methods 0.000 claims 3
- 230000007017 scission Effects 0.000 claims 3
- 229910000831 Steel Inorganic materials 0.000 claims 1
- 239000010959 steel Substances 0.000 claims 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims 1
- 229910052721 tungsten Inorganic materials 0.000 claims 1
- 239000010937 tungsten Substances 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 238000010504 bond cleavage reaction Methods 0.000 abstract 1
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 60
- -1 N- (2-aminoethyl) -beta-alanine ester Chemical class 0.000 description 18
- 238000009472 formulation Methods 0.000 description 13
- 238000002844 melting Methods 0.000 description 13
- 230000008018 melting Effects 0.000 description 13
- 239000004814 polyurethane Substances 0.000 description 13
- 229920002635 polyurethane Polymers 0.000 description 13
- 239000002356 single layer Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000000137 annealing Methods 0.000 description 7
- 229920006037 cross link polymer Polymers 0.000 description 7
- 230000004927 fusion Effects 0.000 description 6
- 239000008365 aqueous carrier Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229920000126 latex Polymers 0.000 description 5
- 239000004816 latex Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000007639 printing Methods 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 150000003869 acetamides Chemical class 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 239000006184 cosolvent Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 229910001092 metal group alloy Inorganic materials 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 3
- 229940083957 1,2-butanediol Drugs 0.000 description 2
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 description 2
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 description 2
- 229910000952 Be alloy Inorganic materials 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 150000003948 formamides Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- 229940015975 1,2-hexanediol Drugs 0.000 description 1
- 229940043375 1,5-pentanediol Drugs 0.000 description 1
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 description 1
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- LCVQGUBLIVKPAI-UHFFFAOYSA-N 2-(2-phenoxypropoxy)propan-1-ol Chemical compound OCC(C)OCC(C)OC1=CC=CC=C1 LCVQGUBLIVKPAI-UHFFFAOYSA-N 0.000 description 1
- XYVAYAJYLWYJJN-UHFFFAOYSA-N 2-(2-propoxypropoxy)propan-1-ol Chemical compound CCCOC(C)COC(C)CO XYVAYAJYLWYJJN-UHFFFAOYSA-N 0.000 description 1
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- RUPBZQFQVRMKDG-UHFFFAOYSA-M Didecyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC RUPBZQFQVRMKDG-UHFFFAOYSA-M 0.000 description 1
- 240000002989 Euphorbia neriifolia Species 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- NBJODVYWAQLZOC-UHFFFAOYSA-L [dibutyl(octanoyloxy)stannyl] octanoate Chemical compound CCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCC NBJODVYWAQLZOC-UHFFFAOYSA-L 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- PSWOBQSIXLVPDV-CXUHLZMHSA-N chembl2105120 Chemical compound C1=C(O)C(OC)=CC(\C=N\NC(=O)C=2C=CN=CC=2)=C1 PSWOBQSIXLVPDV-CXUHLZMHSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- FHKSXSQHXQEMOK-UHFFFAOYSA-N hexane-1,2-diol Chemical compound CCCCC(O)CO FHKSXSQHXQEMOK-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000003906 humectant Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000002492 water-soluble polymer binding agent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/165—Processes of additive manufacturing using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/103—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing an organic binding agent comprising a mixture of, or obtained by reaction of, two or more components other than a solvent or a lubricating agent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/107—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing organic material comprising solvents, e.g. for slip casting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
- B22F1/147—Making a dispersion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/10—Formation of a green body
- B22F10/14—Formation of a green body by jetting of binder onto a bed of metal powder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F12/00—Apparatus or devices specially adapted for additive manufacturing; Auxiliary means for additive manufacturing; Combinations of additive manufacturing apparatus or devices with other processing apparatus or devices
- B22F12/10—Auxiliary heating means
- B22F12/13—Auxiliary heating means to preheat the material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
- B29C64/295—Heating elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
- C08G18/8067—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds phenolic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/35—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2304/00—Physical aspects of the powder
- B22F2304/10—Micron size particles, i.e. above 1 micrometer up to 500 micrometer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2505/00—Use of metals, their alloys or their compounds, as filler
- B29K2505/08—Transition metals
- B29K2505/12—Iron
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
- C08K3/11—Compounds containing metals of Groups 4 to 10 or of Groups 14 to 16 of the Periodic Table
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Optics & Photonics (AREA)
- Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Structural Engineering (AREA)
- Civil Engineering (AREA)
- Ceramic Engineering (AREA)
- Dispersion Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
The present disclosure describes three-dimensional printing packages, systems for three-dimensional printing, and methods of three-dimensional printing. In one example, a three-dimensional printing kit may include a particulate build material and a binder. The particulate build material may include metal particles. The binder may include a polyol and a water-dispersible blocked polyisocyanate having a plurality of blocked isocyanate groups. The blocked isocyanate groups may include blocking groups bonded to carbon atoms of the blocked isocyanate groups via labile bonds that may be broken by heating to a deblocking temperature. Labile bond cleavage can produce a released blocking group that reacts with hydrogen and isocyanate groups.
Description
Background
Three-dimensional (3D) printing may be an additive printing method for manufacturing three-dimensional solid parts from digital models. Three-dimensional printing is commonly used for rapid product prototyping, mold creation, master creation, and short-term manufacturing. Some 3D printing techniques are considered additive methods because they involve applying a continuous layer of material. This is different from other processes, which typically rely on removal of material to create the final part. Some 3D printing methods use chemical binders or adhesives to bond the build materials together. Other 3D printing methods involve partial sintering, melting, etc. of the build material. For some materials, partial melting may be achieved using heat assisted extrusion, and for other materials, curing or fusing may be achieved using, for example, ultraviolet light or infrared light.
Brief description of the drawings
FIG. 1 illustrates an exemplary three-dimensional printing package according to the present disclosure;
FIG. 2 illustrates an exemplary three-dimensional printing package after decapsulation in accordance with the disclosure;
FIG. 3 is a schematic illustration of a curing reaction of particulate build material with binder in an exemplary three-dimensional printing kit according to the present disclosure;
FIG. 4 is a diagrammatic view of a three-dimensional printing system according to the present disclosure; and
fig. 5 is a flow chart illustrating an exemplary three-dimensional printing method according to the present disclosure.
Detailed Description
The present disclosure describes three-dimensional printing suites, systems, and methods. In one example, a three-dimensional printing kit may include a particulate build material and a binder. The particulate build material may include metal particles. The binder may include a polyol and a water-dispersible blocked polyisocyanate having a plurality of blocked isocyanate groups having the chemical structure:
wherein B is a blocking group bonded to a carbon atom of the blocked isocyanate group via an labile bond that can be broken by heating to a deblocking temperature. The labile bond breaks to produce a released blocking group that reacts with hydrogen and isocyanate groups. In other examples, the metal particles may include titanium, cobalt, chromium, nickel, vanadium, tungsten carbide, tantalum, molybdenum, copper, gold, silver, iron alloys, stainless steel, high carbon steel, tool steel, alloys thereof, or mixtures thereof. In still other examples, the metal particles may have a D50 particle size distribution value of about 2 μm to about 100 μm. In certain examples, the water-dispersible blocked polyisocyanate may have an average of 3 to 10 blocked isocyanate groups per molecule. In other examples, the water-dispersible blocked polyisocyanate may include hydrophilic dispersing groups. In still other examples, the deblocking temperature may be about 100 ℃ to about 200 ℃. In some examples, the released blocking group may include a phenol, a pyridinol, a thiophenol, a mercaptopyridine, an alcohol, a thiol, a lactam, an oxime, an amide, an imide, an azole, an imidazole, a pyrazole, a diketene, a formate, or a combination thereof. In one particular example, the binder can include the polyhydroxy polyol in an amount of about 1 wt% to about 15 wt% and the water-dispersible blocked polyisocyanate in an amount of about 1 wt% to about 25 wt% relative to the total weight of the binder. In another example, the total moles of blocked isocyanate groups in the binder may be about 105 to 120 mole percent of the total moles of hydroxyl groups of the polyhydroxy polyol present in the binder.
The present disclosure also describes a system for three-dimensional printing. In one example, a system for three-dimensional printing may include a granular build material, a build material applicator for distributing a layer of the granular build material onto a support bed, and a fluid ejector connected to a binder and positioned to eject the binder onto the layer of granular build material. The build material may include metal particles. The binder may include a polyhydroxy polyol, and a water-dispersible blocked polyisocyanate having a plurality of blocked isocyanate groups having the chemical structure:
wherein B is a blocking group bonded to a carbon atom of the blocked isocyanate group via an labile bond that can be broken by heating to a deblocking temperature. The labile bond breaks to produce a released blocking group that reacts with hydrogen and isocyanate groups. In another example, the system may include a heater positioned to heat the layer of particulate build material and the binder on the layer of particulate build material to a deblocking temperature.
The present disclosure also describes a method of three-dimensional printing. In one example, a method of three-dimensional printing may include repeatedly applying a single layer of build material of a particulate build material comprising metal particles to a support bed. According to the 3D object model, a binder may be selectively applied to the individual layers of build material to define individually patterned layers that are bonded together to form the 3D green object. The binder may include a polyol and a water-dispersible blocked polyisocyanate having a plurality of blocked isocyanate groups having the chemical structure:
Wherein B is a blocking group bonded to a carbon atom of the blocked isocyanate group via an labile bond that can be broken by heating to a deblocking temperature. The labile bond breaks to produce a released blocking group that reacts with hydrogen and isocyanate groups. In one particular example, the adhesive may be applied by a hot fluid injector. In another example, the method may include heating the 3D green object to a deblocking temperature. The deblocking temperature may be about 100 ℃ to about 200 ℃. In yet another example, the method may further include sintering the 3D green object at a sintering temperature of about 500 ℃ to about 3,500 ℃ to fuse the metal particles together and form a sintered 3D object.
The three-dimensional (3D) printing materials and methods described herein may be used to form metallic 3D printed objects from metallic powder build materials. The 3D printing methods described herein may involve applying successive layers of particulate build material with a chemical binder or adhesive printed thereon to bond the successive layers of particulate build material together. In some methods, applying a binder may be employed to form a green object, and then a fused three-dimensional physical object may be formed therefrom. More specifically, a binder may be selectively applied to a layer of particulate build material on a support bed to pattern selected areas of the layer, and then another layer of particulate build material is applied thereon. The binder may be applied to the next layer of granular build material and these processes may be repeated to form a green part (also referred to as a 3D green body or object) which may then be heat fused to form a sintered 3D object.
Binders comprising polymers (e.g., water-soluble polymers or latex) may be used to bind the metal particles together to form a green body. The binder may comprise, for example, a liquid carrier and a polymeric binder. The polymeric binder may be dissolved or dispersed in a liquid carrier (e.g., an aqueous carrier) that is suitable for spraying from a fluid-spraying applicator. In some cases, the binder has been sprayed onto a layer of metal particulate build material and then heated sufficiently to evaporate water from the binder. After stacking a number of layers in this manner, a green body with a low water content can be formed, allowing the polymer from the binder to hold the metal particles together. However, in many cases, the green body can be very fragile at this point. The green body may be very porous and have many pores. Because the green body is fragile, it can be difficult to remove the green body from the surrounding powder in the powder bed without damaging the green body.
The present disclosure describes a binder comprising a polyol and a water-dispersible blocked polyisocyanate having a plurality of blocked isocyanate groups. Such binders can have good jetting properties because the polyhydroxy polyol and the water-dispersible blocked polyisocyanate are not polymerized as yet as the binder is jetted onto the particulate build material. The binder may be sprayed onto the layer of particulate build material, and the layer of particulate build material may then be heated to a deblocking temperature, such as a temperature of about 100 ℃ to about 200 ℃. In general, heating to the deblocking temperature may be performed on a single layer, or the green body may be first formed in bulk form, and then the entire green body may be heated to the deblocking temperature. At this deblocking temperature, the blocking groups of the isocyanate groups of the blocked polyisocyanate are removed. The isocyanate groups may then be reacted with the hydroxyl groups of the polyhydric polyol. Because the polyisocyanate molecule has multiple isocyanate groups, the polyisocyanate and the polyhydroxy polyol can react to form a crosslinked polymer network around the metal particles. The crosslinked polymer may make the green body stronger and more resistant to damage than other polymeric binders.
It is noted that when three-dimensional printing packages, methods of three-dimensional printing, and/or systems for three-dimensional printing are discussed herein, these discussions may be considered to apply to each other, whether or not they are explicitly discussed in the context of this example. Thus, for example, when discussing metal particles in relation to a three-dimensional printing suite, such disclosure is also relevant and directly supported in the context of a three-dimensional printing method, a system for three-dimensional printing, and vice versa.
It will be further understood that terms used herein will assume their ordinary meaning in the relevant art, unless otherwise indicated. In some cases, there are terms that are more specifically defined throughout the specification or that are included at the end of the specification, and thus, these terms may have the meanings described herein.
Three-dimensional printing set
In accordance with an example of the present disclosure, a three-dimensional printing kit 100 is shown in fig. 1. The three-dimensional printing kit may include a binder 106, and a particulate build material 110 that may contain metal particles 104. The binder, shown as droplets applied to the particulate build material in fig. 1 as an example, may be packaged or packaged with the particulate build material in a separate container, and/or the binder may be loaded with the particulate build material in a system for three-dimensional printing.
FIG. 2 shows build material 110 after the binder has been applied and heated to a deblocking temperature to form crosslinked polymer 206. The crosslinked polymer holds the metal particles 104 together. At this point, the metal particles bonded together by the crosslinked polymer may be a green body prepared for sintering, or additional layers of metal particles and binder may be added to form the green body. In some examples, a layer of metal particles may be sprayed with a binder and then heated to form a crosslinked polymer. In other examples, a single layer of metal particles may be sprayed with the binder without heating the layer to the deblocking temperature. The entire green body may be formed in this manner and subsequently heated to the deblocking temperature. In some cases, heating the entire green body to the deblocking temperature in this manner may further strengthen the green body by promoting cross-linking between individual layers of build material.
Build material
The build material contained in the three-dimensional printing kits described herein may be a particulate build material comprising metal particles. The particulate build material may include any type of metal particles that can be fused together at a fusion temperature (above the temperature at which the green body is formed, and above the deblocking temperature). Fusion may be performed by sintering, annealing, melting, etc. the metal particles in the particulate build material together. In one example, the particulate build material may include about 80 wt% to 100 wt% metal particles based on the total weight of the particulate build material.
In one example, the metal particles may be a single phase metal material composed of one element. In such an example, the fusing (e.g., sintering, annealing, etc.) may occur at a temperature below the melting point of the elements of the single-phase metallic material. In other examples, the build material particles may be composed of two or more elements, which may be in the form of a single-phase metal alloy (e.g., the various particles may be alloys), or may be in the form of a multi-phase metal alloy (e.g., the different particles may include different metals). In these examples, the fusing may generally occur over a range of temperatures. As for the alloy, a material having a metal alloy to a nonmetal (e.g., a metal-metalloid alloy) may also be used.
In some examples, the metal particles may include particles of elemental metals or alloys of titanium, cobalt, chromium, nickel, vanadium, tungsten carbide, tantalum, molybdenum, copper, gold, silver, iron alloys, stainless steel, high carbon steel, tool steel, alloys thereof, or mixtures thereof. In one example, the metal particles may be stainless steel.
The D50 particle size of the metal particles may be about 2 μm to equal to or less than about 100 μm. In some examples, the particles may have a D50 particle size distribution value, which may be about 10 to about 100 [ mu ] m, about 20 to about 100 [ mu ] m, about 15 to about 90 [ mu ] m, or about 50 to about 100 [ mu ] m. Individual particle sizes may be outside of these ranges, as "D50 particle size" is defined as the following particle size: at this particle size, half of the particles are larger than the D50 particle size and about half of the other particles are smaller than the particle size of the D50 particle size (by weight based on the metal particle content of the particulate build material).
As used herein, particle size may refer to the diameter value of a spherical particle, or in particles that are not spherical, may refer to the longest dimension of the particle. The particle size may appear as a gaussian or gaussian-like distribution (or a normal or normal-like distribution). The gaussian-like distribution is the following distribution curve: the profile may be Gaussian in its profile shape, but it may be slightly skewed in one direction or the other (toward the smaller or larger end of the particle size distribution range). That is, an exemplary gaussian-like distribution of metal particles may be generally characterized using "D10", "D50", and "D90" particle size distribution values, where D10 refers to the particle size at the 10 th percentile, D50 refers to the particle size at the 50 th percentile, and D90 refers to the particle size at the 90 th percentile. For example, a D50 value of 25 μm means that 50% of the particles (by number) have a particle size of more than 25 μm and 50% of the particles have a particle size of less than 25 μm. The particle size distribution value is not necessarily related to a gaussian distribution curve, but in one example of the present disclosure, the metal particles may have a gaussian distribution, or more typically a gaussian-like distribution with an offset peak at about D50. In practice, a true Gaussian distribution is not generally present, as there may be some skew, but a Gaussian-like distribution may still be considered as a "Gaussian" as used in practice. The particle shape of the particulate build material may be spherical, non-spherical, random, or a combination thereof.
Adhesive agent
The binder may include a polyol and a water-dispersible blocked polyisocyanate having a plurality of blocked isocyanate groups. The polyol may also be water dispersible. The blocked isocyanate groups may have the following chemical structure:
wherein B is a blocking group bonded to a carbon atom of the blocked isocyanate group via an labile bond that can be broken by heating to a deblocking temperature. The labile bond can be broken to produce a released blocking group that reacts with hydrogen and isocyanate groups. In other words, the C-B bond may be broken by heating to the deblocking temperature. the-B group abstracts the H atom bound to the N atom, becomes a released blocking group (BH) that reacts with hydrogen and forms an n=c double bond, yielding an isocyanate group (-n=c=o). After the isocyanate groups are deblocked in this manner, the isocyanate groups can react with the hydroxyl groups of the polyhydroxy polyol to form a polyurethane polymer. Multiple isocyanate groups on a single polyisocyanate molecule can react in this manner to form a crosslinked polyurethane polymer. In some examples, the water-dispersible blocked polyisocyanate may have an average of 3 to 10 blocked isocyanate groups per molecule.
In other examples, the blocked polyisocyanate may include hydrophilic dispersing groups to enhance the dispersibility of the blocked polyisocyanate in water. In some examples, the hydrophilic dispersing group may be anionic or nonionic. Non-limiting examples of hydrophilic dispersing groups may include polyethylene oxide, carboxylic acid groups or carboxylate groups, sulfonic acid groups or sulfonate groups, phosphonic acid groups or phosphonate groups, and the like.
The blocking group attached to the isocyanate group may be any group attached via an labile bond that can be broken by heating to a deblocking temperature. In certain examples, blocking groups (and/or released blocking groups BH that react with hydrogen) may include combinations thereof. In some examples, these blocking groups may be released from the isocyanate groups at a deblocking temperature of about 100 ℃ to 200 ℃. Various combinations of polyisocyanate compounds with different blocking groups may have different deblocking temperatures. In general, the deblocking temperature may be lower than the temperature at which the particulate build material sinters together.
One example of a suitable blocked polyisocyanate trimer has the structure shown below:
Wherein R is independently C2 to C10 branched or straight chain alkyl, C6 to C20 cycloaliphatic, C6 to C20 aromatic, or a combination thereof; and Z is (BL) 3-X (DL) X Wherein BL is selected from the group consisting of a phenol blocking group, a lactam blocking group, an oxime blocking group, an azole blocking group, a diketene blocking group, a formate blocking group, and combinations thereof; x is 0 to 1; and DL is an anionic or nonionic hydrophilic dispersing group such as polyethylene oxide, carboxylic acid group, sulfonic acid group, or the like. Thus, Z independently comprises a blocking group (the "BL" group described herein), a hydrophilic dispersing group (the "DL" group described herein), or a combination of both. In some examples, the three independent Z groups shown in the above formula may represent 2 to 3 blocking groups (BL) and 0 to 1 hydrophilic dispersing groups (DL) per trimer molecule. Thus, in particular reference to Z in formula (la), there may be some specific single molecules of blocked polyisocyanates having three BL groups, as well as other single molecules comprising less than three BL groups. Thus, in some examples, no hydrophilic dispersing groups may be present, and in other examples, from 0.1 to 1 hydrophilic dispersing groups may be present.
Non-limiting examples of commercially available anionic water-dispersible blocked polyisocyanates include IMPLAFIX 2794 from Covesro (HDI trimer blocked with 3, 5-dimethylpyrazole and further comprising N- (2-aminoethyl) -beta-alanine ester; acid number 10 mg KOH/g) and BAYHYDUR BL XP 2706 from Covesro (blocked aliphatic polyisocyanate, acid number 32 mg KOH/g) (Covesro AG, germany). The IMPRAFIX 2794 can be decapsulated at about 130 ℃. Non-limiting examples of commercially available nonionic blocked polyisocyanates that may be used include Matsui FIXER ™ WF-N (3, 5-dimethylpyrazole nonionic blocked polyisocyanate) from Matsui Shikiso Chemical (Matsui Shikiso Chemical, japan) and TRIXENE Aquar BI 220 (nonionic aliphatic water dispersed blocked isocyanate) from Baxenden (Baxenden Chemicals Limited, UK). Matsui FIXER ™ WF-N can be unsealed at about 150 ℃. Additional examples of blocked polyisocyanates that may be used include BAYHYDUR (BL 2867), BAYHYDUR (BL 2781), BAYHYDUR (BL 5335), BAYYBOND (XL 6366) XP, BAYBOND (XL 825), BAYBOND (XL 7270), BAYBOND (XL 3674 XP), or VESTANAT (EP-DS 1205E) and VESTANAT (EP-DS 1076 (Evonik Industries AG, germany) from Covestro.
The polyol used in the binder may be any water-soluble or water-dispersible polyol. In some examples, the polyhydroxy polyol may include polyhydroxy polyesters, polyhydroxy polyurethanes, polyhydroxy polyethers, polycarbonate diols, and hydroxyl-containing polymers, such as polyhydroxy polyacrylates, polyacrylate polyurethanes, polyurethane polyacrylates, or combinations thereof. In other examples, the polyhydroxy polyol may be cationic, anionic, or nonionic. Non-limiting examples of commercially available polyhydroxy polyols that may be used include Bayhydrol A145, A2058, A2227/1, A242, A2427, A2542, A2546, A2601, A2646, A2651, A2695, AXP2770, A2845XP, A2846XP, U241, U355, U475, UXP2750, U2757, UXP2766, UXP7110E, and combinations thereof (Covestro AG, germany).
When the binder is applied to the particulate build material and then heated to a deblocking temperature, the blocked polyisocyanate may deblock and react with the polyhydroxy polyol to form a crosslinked polymer that binds the particulate build material together. Fig. 3 shows a schematic example of this method. In the figure, blocked polyisocyanate 310 is unblocked by heating at a unblocking temperature. The deblocked polyisocyanate 320 is then reacted with the polyol 330 in the presence of the particulate build material particles 340. The result is a crosslinked polyurethane polymer network 350 between and around particles of particulate build material that includes particulate build material associated with the reaction product of the deblocked polyisocyanate and the polyol. In some examples, such cross-linked polyurethane binders may impart greater strength to the green body than other types of binders, such as latex binders or water-soluble polymer binders. In certain examples, the binders described herein may be free of binders other than blocked polyisocyanates and polyhydroxy polyols. In other examples, the binder may be latex-free.
In some examples, the binder may include the polyhydroxy polyol in an amount of about 1 wt.% to about 15 wt.%, based on the total weight of the binder. In other examples, the binder may include the polyhydroxy polyol in an amount of about 2 wt.% to about 12 wt.%, or about 2 wt.% to about 10 wt.%, or about 4 wt.% to about 8 wt.%. In still other examples, the binder may include the water-dispersible blocked polyisocyanate in an amount of about 1 wt% to about 25 wt%, or about 2 wt% to about 20 wt%, or about 5 wt% to about 15 wt%. In certain examples, the amount of polyhydroxy polyol to water-dispersible blocked polyisocyanate may be selected based on the relative amounts of hydroxyl groups in the polyol and blocked isocyanate groups in the blocked polyisocyanate. In one example, the amounts of water-dispersible blocked polyisocyanate and polyol can be selected such that the binder comprises a molar excess of blocked isocyanate groups over hydroxyl groups. In some cases, the moles of the commercially available blocked polyisocyanate to the commercially available polyol can be calculated based on the equivalents provided by the manufacturer. In one particular example, the total moles of blocked isocyanate groups in the binder can be from about 105 mole% to 120 mole% of the total moles of hydroxyl groups of the polyhydroxy polyol present in the binder.
The binder may also comprise an aqueous carrier suitable for spraying. In one example, the aqueous carrier may comprise water as the primary solvent, e.g., the solvent is present at the highest concentration compared to other co-solvents. In addition to water, the aqueous carrier may include one or more organic co-solvents, such as high boiling solvents and/or humectants, for example, aliphatic alcohols, aromatic alcohols, alkyl glycols, glycol ethers, polyglycol ethers, 2-pyrrolidone, caprolactam, formamide, acetamides, and long chain alcohols. Some other more specific exemplary organic co-solvents that may be included in the binder may include aliphatic alcohols, 1, 2-alcohols, 1, 3-alcohols, 1, 4-alcohols, 1, 5-alcohols, 1, 6-alcohols, ethylene glycol alkyl ethers, propylene glycol alkyl ethers, higher homologs of polyethylene glycol alkyl ethers (C6-C12), N-alkyl caprolactams, unsubstituted caprolactams, substituted formamides, unsubstituted formamides, substituted acetamides, unsubstituted acetamides, and combinations thereof. Examples of the water-soluble high boiling point solvent may include propylene glycol ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, dipropylene glycol monophenyl ether, 2-pyrrolidone, 2-methyl-1, 3-propanediol, 1, 2-butanediol, 1, 4-butanediol, 1, 2-pentanediol, 1, 5-pentanediol, 1, 2-hexanediol, 1, 6-hexanediol, methyl pyrrolidone, ethyl pyrrolidone, and the like. The one or more organic co-solvents may add up to 0% to about 50% by weight of the binder. In some examples, the co-solvent may be present at about 5% to about 25%, about 2% to about 20%, or about 10% to about 30% by weight of the binder. In other examples, the co-solvent may be present in about 0 wt% to about 50 wt%, about 5 wt% to about 25 wt%, about 2 wt% to about 20 wt%, or about 10 wt% to about 30 wt% of the total solvent in the binder.
The aqueous carrier may be present in the binder from about 20 wt% to about 98 wt%, from about 70 wt% to about 98 wt%, from about 50 wt% to about 90 wt%, or from about 25 wt% to about 75 wt%. In some examples, the binder may further comprise from about 0.1 wt% to about 50 wt% of other liquid carrier components. These liquid carrier components may include other organic cosolvents, additives that inhibit the growth of harmful microorganisms, viscosity modifiers, pH adjusters, chelating agents, surfactants, preservatives, and the like.
Some examples of liquid carrier components that may inhibit the growth of harmful microorganisms that may be present may include biocides, fungicides, and other microbial agents. Commercially available examples may include ACTICIDE (Thor GmbH, germany), NUOSEPT (Troy, corp., new jersey), UCARCIDE ™ (Dow, michigan), VANCIDE (r.t. Vanderbilt co., ct), PROXEL (Arch Chemicals, inc., ct) and combinations thereof.
In other examples, the binder may also include a catalyst to promote polymerization of the polyisocyanate and the polyol. In certain examples, the catalyst may include tin carboxylates such as dibutyltin dilaurate or dibutyltin dioctoate, bismuth carboxylates, zinc carboxylates, chelates of zirconium and aluminum, tertiary amines such as triethylenediamine, N, N, N ', N ' ', N ' ' -pentamethyldiethylenetriamine, 1, 2-dimethylimidazole, or 1, 4-diazabicyclo [2.2.2] octane (DABCO).
The crosslinked polyurethane polymer formed from the binder may be subjected to a pyrolysis or burn-out process in which the polymer is removed during sintering or annealing. This may occur when thermal energy applied to the green part or object removes inorganic or organic volatiles and/or other materials that may be present either by decomposition or by burning the polymer.
System for three-dimensional printing
The present disclosure also extends to a system for three-dimensional printing. The system may generally include the particulate build material described above with a binder. The particulate build material may be distributed in a single layer by a build material applicator, and the binder may be sprayed onto the layer by a fluid sprayer. Fig. 4 shows an exemplary system 400 for three-dimensional printing according to the present disclosure. The system includes a build platform 402. Particulate build material 410 may be deposited onto the build platform by build material applicator 408, where the particulate build material may be leveled or smoothed, for example, by mechanical rollers or other leveling techniques. This may form a planar layer of particulate build material. The adhesive 406 may then be applied to the layer by fluid ejector 414. The area 424 to which the adhesive is applied may correspond to a layer or slice of the 3D object model. The system may also include a heater 412 that may apply heat to the layer of particulate build material and binder that has been applied. The heater may heat the build material and the binder to a deblocking temperature to initiate a reaction that produces the crosslinked polyurethane polymer, thereby binding the particulate build material together. This may form a solid green layer 426. In fig. 4, a green layer has been formed and then a new layer of particulate build material has been laid down on the first green layer. After jetting the individual layers with the binder, the build platform may be lowered a distance (x) that may correspond to the thickness of the printed layers to provide space for new layers of particulate build material. The figure shows the binder sprayed onto the new layer of particulate build material. After the green body is fully printed, the green body may be fused (e.g., sintered, annealed, etc.) in an oven 430.
As used herein, "applying a single layer of particulate build material onto a support bed" may include applying a first layer of particulate build material directly onto an empty support bed. The "support bed" may refer to a build platform, for example as shown in fig. 4. Further, in some examples, one or more layers of granular build material may be laid down on the support bed without spraying any binder onto the layers. This may provide a hotter uniform temperature distribution for the first layer to have adhesive sprayed thereon. Thus, "applying a single layer of particulate build material onto a support bed" may include applying a layer of particulate build material onto an initial layer or layers that may be applied without any binder. The phrase "applying individual layers of build material of particulate build material onto a support bed" also includes application to subsequent layers when layers or slices of green body have been formed in the underlying layers.
In other examples, the system may include a heater. The heater may be placed above the granular build material as in fig. 4, or in other examples, the heater may be on one or more sides of the granular build material, below the granular build material, or a combination of these locations. In some examples, the support bed may include an integrated heater to heat the granular build material from below. The heating may heat the particulate build material to a deblocking temperature to deblock the blocked polyisocyanate, and/or to a temperature sufficient to evaporate the solvent from the binder. In some examples, the heater may include a resistive heater, a heating lamp, an infrared heater, a halogen lamp, a fluorescent lamp, an oven, or other type of heater.
Three-dimensional printing method
A flowchart of an exemplary method 500 of three-dimensional (3D) printing is shown in fig. 5. The method comprises the following steps: repeatedly applying a single layer of build material comprising particulate build material of metal particles to a support bed 510; and selectively applying a binder to the individual layers of build material according to the 3D object model to define individually patterned layers that are bonded together to form a 3D green object, wherein the binder comprises:
polyhydroxy polyol, and
a water-dispersible blocked polyisocyanate having a plurality of blocked isocyanate groups having the chemical structure:
wherein B is a blocking group bonded to a carbon atom of the blocked isocyanate group via an labile bond that can be broken by heating to a deblocking temperature, wherein breaking the labile bond produces a released blocking group 520 that reacts with hydrogen and the isocyanate group. The particulate build material comprising metal particles and binder and related systems may be, for example, those previously described.
In more detail, repeatedly applying the single layer of build material of the particulate build material may include applying the single layer of build material at a thickness that may be from about 1 [ mu ] m to about 150 [ mu ] m, from about 20 [ mu ] m to about 150 [ mu ] m, from about 10 [ mu ] m to about 100 [ mu ] m, from about 25 [ mu ] m to about 75 [ mu ] m, from about 10 [ mu ] m to about 50 [ mu ] m, or from about 50 [ mu ] m to about 125 [ mu ] m. In some examples, the single layer of build material may have a thickness of about 1 μm to about 100 μm.
The adhesive may be selectively printed by a fluid ejector. In some examples, the fluid ejector may be a printhead, which may be a piezoelectric printhead, a thermal inkjet printhead, or a continuous inkjet printhead. After printing the individual layers of build material with the binder, in some cases, the individual layers of build material may be heated to drive off moisture and further cure the layers of the 3D green body. The build platform may be lowered by a distance (x) that may correspond to the thickness of the printed layer of the 3D green object so that another layer of granular build material may be added thereto, printed with a binder, cured, and the like. The process may be repeated on a layer-by-layer basis until the entire 3D green object is formed, which is stable enough to move to an oven suitable for fusing (e.g., sintering, annealing, melting, etc.).
In some examples, heat may be applied to a single layer (or group of layers) of build material having a binder printed on the single layer (or group of layers) of build material to drive off moisture from the binder and further cure the single layer of build material of the 3D green body. In other examples, the heat may be sufficient to heat the build material to a deblocking temperature to deblock the blocked polyisocyanate in the binder. In one example, heat may be applied from above the granular build material and/or may be provided by the build platform from below the granular build material. In some examples, the particulate build material may be heated prior to dispensing. In addition, the heating may be performed while applying the adhesive to the individual layers of build material or after applying all of the printed adhesive. One or more temperatures at which the metal particles of the particulate build material fuse together are higher than the ambient temperature of the patterned portion in which the 3D printing process is performed, e.g., patterning occurs at about 18 ℃ to about 300 ℃, and fusing occurs at about 500 ℃ to about 3,500 ℃. In some examples, the metal particles of the particulate build material may have a melting point of about 500 ℃ to about 3,500 ℃. In other examples, the metal particles of the particulate build material may be alloys having a range of melting points.
Thus, after forming the 3D green body, the entire 3D green body may be moved to an oven and heated to a temperature of about 500 ℃ to about 3,500 ℃, or more typically about 600 ℃ to about 1,500 ℃, in order to fuse the metal particles together and form a sintered 3D body. In some examples, the temperature may be about 600 ℃ to about 1,200 ℃, about 800 ℃ to about 1,200 ℃, or about 750 ℃ to about 1,500 ℃. In one example, depending on the metal particles, these temperature ranges may be used for the outer layer of the molten metal particles and may allow the metal particles to sinter to one another without melting the inner portion of the metal particles.
The final sintering temperature range may vary depending on the material, but in one example, the sintering temperature may be about 10 ℃ below the melting temperature of the metal particles of the particulate build material to about 50 ℃ below the melting temperature of the metal particles of the particulate build material. The sintering temperature may also depend on the particle size and the time for heating to occur, e.g., at an elevated temperature for a time sufficient to cause the particle surfaces to become physically fused or composited together. For example, the sintering temperature of the stainless steel may be about 1400 ℃, and examples of the sintering temperature of the aluminum or aluminum alloy may be about 550 ℃ to about 620 ℃. The sintering temperature may sinter and/or otherwise fuse the metal particles to form a sintered 3D object.
Definition of the definition
It is noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the content clearly dictates otherwise.
The term "about" as used herein when referring to a value or range allows for some degree of variation of the value or range, for example within 10% of the limit of the value or range, or within 5% on the one hand. The term "about" when referring to a numerical range is also understood to include the range defined by the exact numerical value shown as a subrange of values, e.g., a range of about 1 wt.% to about 5 wt.% includes 1 wt.% to 5 wt.% as a explicitly supported subrange.
The phrases "green part," "green," "3D green object," and "layered green" as used herein refer to any intermediate structure prior to any fusing of particles with the particle material, including a 3D green object or one or more layers of a 3D green object, a green 3D support structure or one or more layers of a green 3D support structure, or an intermediate 3D separation interface or one or more intermediate 3D separation interface layers. As a green body, the particulate build material may be bonded together by a binder. Typically, the mechanical strength of the green body is such that the green body may be handled or extracted from the build platform for placement in a fusion oven. It should be understood that any particulate build material that is not patterned with a binder is not considered part of the green body, even if the particulate build material is adjacent to or surrounds the green body. For example, unprinted granular build material may be used to support a green body when received therein, but the granular build material is not part of the green body unless the granular build material is printed with a binder or some other fluid that is used to create a solidified part prior to fusing (e.g., sintering, annealing, melting, etc.).
The terms "3D part", "3D object" and the like are used herein to refer to a target 3D object to be built. The 3D object may be referred to as a "fused" or "sintered" 3D object, indicating that the object has been fused, such as by sintering, annealing, melting, etc., or as a "green body" or "green" 3D object, indicating that the object has solidified but has not yet been fused.
As used herein, a "kit" may be synonymous with and understood to include multiple compositions comprising multiple components, where the different compositions may be separately contained in the same container or containers prior to and during use (e.g., building a 3D object), but the components may be combined together during the building process. The container may be any type of vessel, box or receptacle made of any material.
The terms "fuse", "fusion" and the like refer to the joining of materials of adjacent particles of particulate build material, such as by sintering, annealing, melting, and the like, and may include the complete fusion of adjacent particles into a common structure, e.g., fused together, or may include surface fusion, where the particles are not completely fused to a liquefaction point, but are fused to the following points: which allows individual particles of the particulate build material to become bonded to one another, such as forming material bridges between the particles at or near the points of contact.
As used herein, a plurality of items, structural elements, compositional elements, and/or materials may be presented in a common list for convenience. However, these lists should be construed as though the individual members of the list are identified as separate and distinct members. Thus, no individual member of such list should be construed as a de facto equivalent of any other member of the same list based on their presentation in a common group without indications to the contrary.
Concentrations, dimensions, amounts, and other numerical data may be presented herein in a range format. It is to be understood that such range format is used merely for convenience and brevity and should be interpreted flexibly to include the numerical values explicitly recited as the limits of the range, as well as to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and/or sub-range is explicitly recited. For example, a weight ratio range of about 1 wt% to about 20 wt% should be interpreted to include the explicitly recited limits of 1 wt% and 20 wt%, and to include individual weights such as about 2 wt%, about 11 wt%, about 14 wt%, and sub-ranges such as about 10 wt% to about 20 wt%, about 5 wt% to about 15 wt%, etc.
Examples
Embodiments of the present disclosure are shown below. However, it is to be understood that the following are illustrative of the application of the principles of the present disclosure. Many modifications and alternative compositions, methods, and systems may be devised without departing from the spirit and scope of the present disclosure. The appended claims are intended to cover such modifications and arrangements.
A series of struts are formed from stainless steel powder and a binder. The stainless steel powder and the binder are mixed with a high speed mixer to ensure uniform mixing. The wet powder was dried in a vacuum oven at 30 ℃ for two hours until approximately 80% of the water was removed. 18 grams of this dry powder was poured into the opening of a compression bar mold and compressed at 2000 psi for 30 seconds to form compression bars (50 mm (length), 12mm (width) and 5.5mm (thickness)). The struts were carefully separated from the mold and cured with a slow air stream at 180 ℃ for 30 minutes at a pressure of 22-25 inches hg in a vacuum oven. The solidified struts were cooled and sent to a 3-point bending Instron tester to measure tensile strength.
Several different binder formulations were used to make the struts to compare the tensile strength of the resulting struts. Five struts were made for different strut formulations and the average maximum tensile stress (mPa) and standard deviation were reported.
The blocked polyisocyanate included in the binder formulation was the Imprafix (r) 2794 blocked isocyanate dispersion of Covestro (40% solids in water,% NCO 4.8%). Polyols are different in different formulations. The polyol is from Bayhydrol polyol series based on water. The Bayhydrol polyols used are shown in Table 1.
TABLE 1
Bayhydrol polyol | Type(s) | % solids | %OH | Equivalent weight of |
A 2546 | Acrylic polyols | 41 | 4.8 | 354 |
A 2601 | Acrylic polyols | 45 | 3.9 | 436 |
A 2542 | Acrylic polyols | 50 | 3.8 | 447 |
A 2695 | Acrylic polyols | 41 | 5 | 340 |
A 2846 | Acrylic polyols | 40 | 1.5 | 1133 |
A2646 | Acrylic polyols | 50 | 3.8 | 447 |
UXP 2750 | Polyurethane polyols | 41 | 3.6 | 472 |
UXP 2766 | Polyurethane polyols | 37 | 4 | 425 |
U 2757 | Polyurethane polyols | 52 | 1 | 1700 |
Various binder formulations are shown in table 2. 10 wt% of the Imprafix 2764 is used as blocked polyisocyanate in the formulation. In various formulations, the polyols were different and the amount of polyol was calculated based on the% OH of the polyol reported by the manufacturer such that there was a 10 mole% excess of NCO compared to the moles of OH.
TABLE 2
Ink setNumber of sample/sample | % active | 1 (Compound) | 2 (Compound) | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
1, 2-butanediol | As is | 26.0 | 26.00 | 26.0 | 26.0 | 26.0 | 26.0 | 26.0 | 26.0 | 26.0 | 26.0 |
Tergitol® 15-S-7 | 100 | 0.90 | 0.90 | 0.90 | 0.90 | 0.90 | 0.90 | 0.90 | 0.90 | 0.90 | 0.90 |
Tergitol® TMN-6 | 90 | 0.90 | 0.90 | 0.90 | 0.90 | 0.90 | 0.90 | 0.90 | 0.90 | 0.90 | 0.90 |
Cyan ink | 12.72 | 0.40 | 0.40 | 0.40 | 0.40 | 0.40 | 0.40 | 0.40 | 0.40 | 0.40 | 0.40 |
Reaxis® C708 | 100 | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 |
Latex | 32 | 10 | |||||||||
Imprafix® 2794 | 38.0 | 10.00 | 10.0 | 10.0 | 10.0 | 10.0 | 10.0 | 10.0 | 10.0 | 10.0 | |
Bayhydrol® A-2646 | 50.0 | 4.26 | |||||||||
Bayhydrol® UXP 2766 | 37.0 | 4.05 | |||||||||
Bayhydrol® U XP 2750 | 41.0 | 4.50 | |||||||||
Bayhydrol® A 2695 | 41.0 | 3.24 | |||||||||
Bayhydrol® A-2546 | 41.0 | 3.38 | |||||||||
Bayhydrol® A2601 | 45.0 | 4.15 | |||||||||
Bayhydrol® A 2542 | 50.0 | 4.26 | |||||||||
Bayhydrol® A2846 | 40.0 | 10.75 |
The amounts shown in table 2 are parts by weight as dry content (i.e. the ingredients do not include any water content). Water was then added to obtain a total of 100 parts by weight. The cyan ink was used to visualize the powder mix quality. Imprafix cube 2794 is a commercial blocked isocyanate dispersion from Covestro Chemical Company.
Tergitol 15-S-7 and TMN-6 are surfactants from Dow (Michigan).
Reaxis C708 is a Bi-Zn promoter for polyurethane polymerization from Reaxis, inc.
The compression bar formulation contained 94.8 wt% stainless steel powder and 5.2 wt% binder. The stainless steel powder used in this study was PAC #1009 having an average particle size of 22 μm. Table 3 shows the maximum tensile stress and standard deviation of the cured struts (5 struts with associated adhesive formulations were tested and averaged for maximum tensile stress).
TABLE 3 average maximum tensile stress of the cure struts (cure temperature=180℃)
Sample number | Latex (wt.%) | Imprafix 2764 (wt.%) | Polyol (wt%) | Polyhydroxy polyol | Maximum strength of | STD |
1 (Compound) | 10 | 0 | 0 | Without any means for | 4.0 | 0.1 |
2 (Compound) | 10 | 0 | Without any means for | 4.84 | 0.20 | |
3 | 10 | 4.26 | Bayhydrol® A-2646 | 7.41 | 0.24 | |
4 | 10 | 4.05 | Bayhydrol® UXP 2766 | 11.80 | 0.35 | |
5 | 10 | 4.5 | Bayhydrol® U XP 2750 | 6.60 | 0.32 | |
6 | 10 | 3.24 | Bayhydrol® A 2695 | 9.31 | 0.48 | |
7 | 10 | 3.38 | Bayhydrol® A-2546 | 9.19 | 0.25 | |
8 | 10 | 4.15 | Bayhydrol® A2601 | 10.46 | 0.46 | |
9 | 10 | 4.26 | Bayhydrol® A 2542 | 7.64 | 0.47 | |
10 | 10 | 10.75 | Bayhydrol® A2846 | 10.16 | 0.49 |
Based on these test results, the reaction product of Imprafix 2764 with bayhydro l polyhydroxy polyol can be a very strong binder for metal powders. The formulation tested was stronger than the latex binder used in comparative sample 1. The formulation tested was also stronger than comparative sample 2 (which included Imprafix cube 2764 without any polyol). Of the formulations tested, bayhydrol UXP 2766, A2695, A-2546, A-2601 and A2846 gave the best results, but all formulations were superior to the control samples.
Claims (17)
1. A three-dimensional printing kit comprising:
a particulate build material comprising metal particles; and
a binder, comprising:
polyhydroxy polyol, and
a water-dispersible blocked polyisocyanate having a plurality of blocked isocyanate groups having the chemical structure:
wherein B is a blocking group bonded to a carbon atom of the blocked isocyanate group via an labile bond cleavable by heating to a deblocking temperature, wherein cleavage of the labile bond results in a released blocking group that reacts with hydrogen and the isocyanate group,
wherein the total moles of blocked isocyanate groups in the binder is from 105 mole% to 120 mole% of the total moles of hydroxyl groups of the polyhydroxy polyol present in the binder.
2. The three-dimensional printing kit of claim 1, wherein the metal particles comprise titanium, cobalt, chromium, nickel, vanadium, tungsten, tantalum, molybdenum, copper, gold, silver, iron alloys, or mixtures thereof.
3. The three-dimensional printing kit of claim 1, wherein the metal particles comprise steel.
4. The three-dimensional printing kit of claim 1, wherein the metal particles comprise stainless steel, high carbon steel, tool steel, or mixtures thereof.
5. The three-dimensional printing kit of claim 1, wherein the metal particles have a D50 particle size distribution value of 2 μιη to 100 μιη.
6. The three-dimensional printing kit of claim 1, wherein the water-dispersible blocked polyisocyanate has an average of 3 to 10 blocked isocyanate groups per molecule.
7. The three-dimensional printing kit of claim 1, wherein the water-dispersible blocked polyisocyanate comprises hydrophilic dispersing groups.
8. The three-dimensional printing kit of claim 1, wherein the deblocking temperature is 100 ℃ to 200 ℃.
9. The three-dimensional printing kit of claim 1, wherein the released blocking group comprises a phenol, a mercaptopyridine, an alcohol, a thiol, a lactam, an oxime, an amide, an imide, an azole, a diketene, a formate, or a combination thereof.
10. The three-dimensional printing kit of claim 1, wherein the released blocking group comprises a pyridinol, thiophenol, imidazole, pyrazole, or a combination thereof.
11. The three-dimensional printing kit of claim 1, wherein the binder comprises the polyhydroxy polyol in an amount of 1 wt% to 15 wt% and the water-dispersible blocked polyisocyanate in an amount of 1 wt% to 25 wt%, relative to the total weight of the binder.
12. A system for three-dimensional printing, comprising:
a particulate build material comprising metal particles;
a build material applicator for distributing a layer of particulate build material onto a support bed;
a fluid injector fluidly connected to a binder and positioned to inject the binder onto a layer of particulate build material, wherein the binder comprises:
polyhydroxy polyol, and
a water-dispersible blocked polyisocyanate having a plurality of blocked isocyanate groups having the chemical structure:
wherein B is a blocking group bonded to a carbon atom of the blocked isocyanate group via an labile bond cleavable by heating to a deblocking temperature, wherein cleavage of the labile bond results in a released blocking group that reacts with hydrogen and the isocyanate group,
wherein the total moles of blocked isocyanate groups in the binder is from 105 mole% to 120 mole% of the total moles of hydroxyl groups of the polyhydroxy polyol present in the binder.
13. The system for three-dimensional printing of claim 12, further comprising a heater positioned to heat the layer of particulate build material and the binder on the layer of particulate build material to an unsealing temperature.
14. A method of three-dimensional printing comprising:
repeatedly applying individual layers of build material of a particulate build material comprising metal particles to a support bed;
according to a 3D object model, a binder is selectively applied to individual layers of build material to define individually patterned layers that are bonded together to form a 3D green object, wherein the binder comprises:
polyhydroxy polyol, and
a water-dispersible blocked polyisocyanate having a plurality of blocked isocyanate groups having the chemical structure:
wherein B is a blocking group bonded to a carbon atom of the blocked isocyanate group via an labile bond cleavable by heating to a deblocking temperature, wherein cleavage of the labile bond results in a released blocking group that reacts with hydrogen and the isocyanate group,
wherein the total moles of blocked isocyanate groups in the binder is from 105 mole% to 120 mole% of the total moles of hydroxyl groups of the polyhydroxy polyol present in the binder.
15. The method of three-dimensional printing of claim 14, wherein the adhesive is applied by a hot fluid ejector.
16. The method of three-dimensional printing of claim 14, further comprising heating the 3D green object to a deblocking temperature, wherein the deblocking temperature is 100 ℃ to 200 ℃.
17. The method of three-dimensional printing of claim 14, further comprising sintering the 3D green object at a sintering temperature of 500 ℃ to 3,500 ℃ to fuse metal particles together and form a sintered 3D object.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US2019/023711 WO2020197540A1 (en) | 2019-03-22 | 2019-03-22 | Three-dimensional printing with blocked polyisocyanates |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113490559A CN113490559A (en) | 2021-10-08 |
CN113490559B true CN113490559B (en) | 2023-10-31 |
Family
ID=72609111
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201980093421.4A Active CN113490559B (en) | 2019-03-22 | 2019-03-22 | Three-dimensional printing with blocked polyisocyanates |
Country Status (4)
Country | Link |
---|---|
US (1) | US20220002586A1 (en) |
EP (1) | EP3921103A4 (en) |
CN (1) | CN113490559B (en) |
WO (1) | WO2020197540A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113929869B (en) * | 2021-11-29 | 2022-08-16 | 四川大学 | Two-component polyurea material for 3D printing and method for 3D printing of polyurea product |
CN115785571A (en) * | 2022-12-09 | 2023-03-14 | 万华化学(宁波)有限公司 | 3D printing polypropylene particle for large industrial model and outdoor building and preparation method thereof |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1193277A2 (en) * | 2000-09-27 | 2002-04-03 | Degussa AG | Water dispersable blocked polyisocyanate adducts in powder form, a process for their preparation and their use |
CN1933961A (en) * | 2004-03-22 | 2007-03-21 | 亨斯迈先进材料(瑞士)有限公司 | Photocurable compositions |
US7267928B2 (en) * | 2004-04-19 | 2007-09-11 | Konica Minolta Medical & Graphic, Inc. | Printing plate material and printing process |
CN102947399A (en) * | 2010-06-17 | 2013-02-27 | 惠普发展公司,有限责任合伙企业 | Polyurethane-containing inkjet ink |
WO2017015159A1 (en) * | 2015-07-17 | 2017-01-26 | Applied Materials, Inc. | Selective material dispensing and fusing of multiple layers in additive manufacturing |
CN106687861A (en) * | 2014-06-23 | 2017-05-17 | 卡本有限公司 | Methods of producing three-dimensional objects from materials having multiple mechanisms of hardening |
JP2018041692A (en) * | 2016-09-09 | 2018-03-15 | 東洋紡株式会社 | Ductile conductive composition and method for manufacturing three-dimensional printed wiring board |
CN108885916A (en) * | 2016-03-29 | 2018-11-23 | 东洋纺株式会社 | The manufacturing method of ductility conductivity slurry and curve surface printing wiring board |
WO2019009906A1 (en) * | 2017-07-06 | 2019-01-10 | Hewlett-Packard Development Company, L.P. | Three-dimensional (3d) printing |
-
2019
- 2019-03-22 EP EP19920926.3A patent/EP3921103A4/en active Pending
- 2019-03-22 US US17/054,573 patent/US20220002586A1/en active Pending
- 2019-03-22 CN CN201980093421.4A patent/CN113490559B/en active Active
- 2019-03-22 WO PCT/US2019/023711 patent/WO2020197540A1/en active Application Filing
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1193277A2 (en) * | 2000-09-27 | 2002-04-03 | Degussa AG | Water dispersable blocked polyisocyanate adducts in powder form, a process for their preparation and their use |
CN1933961A (en) * | 2004-03-22 | 2007-03-21 | 亨斯迈先进材料(瑞士)有限公司 | Photocurable compositions |
US7267928B2 (en) * | 2004-04-19 | 2007-09-11 | Konica Minolta Medical & Graphic, Inc. | Printing plate material and printing process |
CN102947399A (en) * | 2010-06-17 | 2013-02-27 | 惠普发展公司,有限责任合伙企业 | Polyurethane-containing inkjet ink |
CN106687861A (en) * | 2014-06-23 | 2017-05-17 | 卡本有限公司 | Methods of producing three-dimensional objects from materials having multiple mechanisms of hardening |
WO2017015159A1 (en) * | 2015-07-17 | 2017-01-26 | Applied Materials, Inc. | Selective material dispensing and fusing of multiple layers in additive manufacturing |
CN108885916A (en) * | 2016-03-29 | 2018-11-23 | 东洋纺株式会社 | The manufacturing method of ductility conductivity slurry and curve surface printing wiring board |
JP2018041692A (en) * | 2016-09-09 | 2018-03-15 | 東洋紡株式会社 | Ductile conductive composition and method for manufacturing three-dimensional printed wiring board |
WO2019009906A1 (en) * | 2017-07-06 | 2019-01-10 | Hewlett-Packard Development Company, L.P. | Three-dimensional (3d) printing |
Also Published As
Publication number | Publication date |
---|---|
EP3921103A4 (en) | 2022-11-02 |
US20220002586A1 (en) | 2022-01-06 |
CN113490559A (en) | 2021-10-08 |
EP3921103A1 (en) | 2021-12-15 |
WO2020197540A1 (en) | 2020-10-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN113490559B (en) | Three-dimensional printing with blocked polyisocyanates | |
US12064898B2 (en) | Particles having a sinterable core and a polymeric coating, use thereof, and additive manufacturing method using the same | |
US11318532B2 (en) | Three-dimensional (3D) printing | |
CN109071986A (en) | Ink group and image recording process | |
CN112409790A (en) | Adhesive composition applied to 3D printing and application method thereof | |
US11541568B2 (en) | Three-dimensional (3D) printing with a detailing agent fluid and a liquid functional material | |
CN108699371A (en) | External member, ink jet printing method, ink-jet printer and the printed article of ink, ink and base material | |
US20190054651A1 (en) | Three-Dimensional (3D) Printing With A Sintering Aid/Fixer Fluid And A Liquid Functional Material | |
JP2013509317A (en) | Printing method | |
CN113453822B (en) | Three-dimensional metal object shaping | |
CN102471665A (en) | Surfactant | |
US20210354203A1 (en) | Three-dimensional printing | |
US11426929B2 (en) | Powder material for producing three-dimensional object, kit for producing three-dimensional object, and three-dimensional object producing method and apparatus | |
CN109642008A (en) | The method for successively constructing molding using the adhesive composition based on phenolic urethanes | |
US20220258238A1 (en) | Three-dimensional printing with austenitic steel particles | |
US20220274173A1 (en) | Three-dimensional printing with stainless steel particles | |
CN112055631B (en) | Three-dimensional printing | |
US20230373004A1 (en) | Three-dimensional printing of metal objects using binding agent with copper nitrate | |
WO2020060541A1 (en) | Three-dimensional printing | |
JP7413755B2 (en) | Decorative metallic luster film ink and method for producing laminate | |
CN114829147B (en) | Three-dimensional printing using wetting agents | |
JP2022103518A (en) | Manufacturing method of molded article | |
WO2022019882A1 (en) | Three-dimensional printing with wetting agent | |
JP2021146668A (en) | Modeling liquid, three-dimensional modeling kit, and method for producing three-dimensional model |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |